EP3959194A1 - Verfahren zur herstellung von verbindungen mit mindestens einer alkylengruppe und mindestens einer thiol- oder thiolatgruppe - Google Patents
Verfahren zur herstellung von verbindungen mit mindestens einer alkylengruppe und mindestens einer thiol- oder thiolatgruppeInfo
- Publication number
- EP3959194A1 EP3959194A1 EP20720449.6A EP20720449A EP3959194A1 EP 3959194 A1 EP3959194 A1 EP 3959194A1 EP 20720449 A EP20720449 A EP 20720449A EP 3959194 A1 EP3959194 A1 EP 3959194A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- compound
- thiol
- groups
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000007944 thiolates Chemical group 0.000 title claims abstract description 27
- 150000003573 thiols Chemical class 0.000 title claims abstract description 23
- 125000002947 alkylene group Chemical group 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title description 5
- 239000007858 starting material Substances 0.000 claims abstract description 42
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 34
- HDFRDWFLWVCOGP-UHFFFAOYSA-M sulfanylformate Chemical group [O-]C(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-M 0.000 claims abstract description 17
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 125000000962 organic group Chemical group 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 125000000320 amidine group Chemical group 0.000 claims description 2
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 2
- 229910052914 metal silicate Inorganic materials 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 2
- 229920000642 polymer Polymers 0.000 description 14
- 229920001021 polysulfide Polymers 0.000 description 12
- 239000005077 polysulfide Substances 0.000 description 12
- 150000008117 polysulfides Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 10
- 238000006114 decarboxylation reaction Methods 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- -1 amino-substituted ethylene thiol Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 3
- PBFKVYVGYHNCGT-UHFFFAOYSA-N 1-sulfanylpropane-1,2,3-triol Chemical compound OCC(O)C(O)S PBFKVYVGYHNCGT-UHFFFAOYSA-N 0.000 description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 description 2
- 229940006190 2,3-dimercapto-1-propanesulfonic acid Drugs 0.000 description 2
- JLVSRWOIZZXQAD-UHFFFAOYSA-N 2,3-disulfanylpropane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(S)CS JLVSRWOIZZXQAD-UHFFFAOYSA-N 0.000 description 2
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 2
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 0.000 description 2
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 2
- DJPWDGITYKJTDN-UHFFFAOYSA-N 3-(2-phenylphenyl)benzene-1,2-dithiol Chemical compound Sc1cccc(c1S)-c1ccccc1-c1ccccc1 DJPWDGITYKJTDN-UHFFFAOYSA-N 0.000 description 2
- QGRVXEOIASZLIL-UHFFFAOYSA-N 3-phenylbenzene-1,2-dithiol Chemical compound SC1=CC=CC(C=2C=CC=CC=2)=C1S QGRVXEOIASZLIL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JLLMOYPIVVKFHY-UHFFFAOYSA-N Benzenethiol, 4,4'-thiobis- Chemical compound C1=CC(S)=CC=C1SC1=CC=C(S)C=C1 JLLMOYPIVVKFHY-UHFFFAOYSA-N 0.000 description 2
- CMXQXXKZIFLESD-UHFFFAOYSA-N C(CCCCCCCCCCC)(=O)OCCC(S)S Chemical compound C(CCCCCCCCCCC)(=O)OCCC(S)S CMXQXXKZIFLESD-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- NNJWFWSBENPGEY-UHFFFAOYSA-N [2-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=CC=C1CS NNJWFWSBENPGEY-UHFFFAOYSA-N 0.000 description 2
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- UNQHMFJVBBWADE-UHFFFAOYSA-N butane-1,1-dithiol Chemical compound CCCC(S)S UNQHMFJVBBWADE-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 2
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical class SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- CDMIYIVDILNBIJ-UHFFFAOYSA-N triazinane-4,5,6-trithione Chemical compound SC1=NN=NC(S)=C1S CDMIYIVDILNBIJ-UHFFFAOYSA-N 0.000 description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- DAJDXKBYZZGECL-UHFFFAOYSA-N 1,3-oxathiolan-2-one Chemical compound O=C1OCCS1 DAJDXKBYZZGECL-UHFFFAOYSA-N 0.000 description 1
- IGZUNAJRZXRCSF-UHFFFAOYSA-N 1-(dibutylamino)ethanethiol Chemical compound CCCCN(C(C)S)CCCC IGZUNAJRZXRCSF-UHFFFAOYSA-N 0.000 description 1
- DYTTUVYNGUXIHE-UHFFFAOYSA-N 1-[2-(dibutylamino)ethylsulfanyl]ethanethiol Chemical compound C(CCC)N(CCCC)CCSC(C)S DYTTUVYNGUXIHE-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YYKVTJNAMNQKIU-UHFFFAOYSA-N 3,3-bis(sulfanyl)propan-1-ol Chemical compound OCCC(S)S YYKVTJNAMNQKIU-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 239000004358 Butane-1, 3-diol Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004146 Propane-1,2-diol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical class OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 239000012455 biphasic mixture Substances 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical class CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UWHMFGKZAYHMDJ-UHFFFAOYSA-N propane-1,2,3-trithiol Chemical compound SCC(S)CS UWHMFGKZAYHMDJ-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical group C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/26—Thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/30—Sulfides having the sulfur atom of at least one thio group bound to two carbon atoms of six-membered aromatic rings
Definitions
- the present invention relates to a process for the synthesis of a compound with at least one alkylene group and at least one thiol or thiolate group, wherein
- thiocarbonate a compound with at least one five-membered cyclic monothiocarbonate group, shortly referred to as thiocarbonate, is reacted with
- a starter selected from compounds with at least one thiol group, from compounds with at least one hydroxy group or from basic inorganic compounds,
- Sulfur compounds and notably sulfur comprising polymers are of interest in many technical applications.
- the sulfur atom contributes notably to properties such as chemical resistance.
- Thiol groups are very reactive. Compounds with thiol groups are therefore valuable
- Polysulfides may be obtained by ring opening polymerization of episulfides, as described in US 3624052 for propylene sulfide polymers.
- US 6525168 B2 a process for the preparation of polysulfides is disclosed, wherein di-halogeno compounds are reacted with dithiols.
- cyclic monothiocarbonates may react with a primary amine under decarboxylation to form an amino-substituted ethylene thiol.
- the ethylene thiol obtained may react with further thiocarbonate under decarboxylation to give a polymer.
- US 3232936 describes a process for mercaptoethylating amines, especially a process for preparing di-n-butylaminoethylmercaptoethanethiol from a mixture of di-n-butylaminoethanethiol and ethylene monothiocarbonate in toluene.
- the present invention relates to a process for the synthesis of a compound with at least one alkylene group and at least one thiol or thiolate group, wherein
- thiocarbonate a compound with at least one five-membered cyclic monothiocarbonate group, shortly referred to as thiocarbonate, is reacted with
- a starter selected from compounds with at least one thiol group, from compounds with at least one hydroxy group or from basic inorganic compounds,
- the process of this invention is a process to obtain a compound with at least one alkylene group and at least one thiol or thiolate group.
- the alkylene group of the compound obtained corresponds to the two carbon atoms of the five- membered cyclic monothiocarbonate group, preferably to the two carbon atoms of the five- membered cyclic monothiocarbonate group as shown in formula (I), see below; in other words, the alkylene group is notably an ethylene group substituted by R 1 to R 4 , see paragraph above.
- the compound with at least one alkylene group and at least one thiol or thiolate group is a polyalkylenesulfide.
- the polyalkylenesulfides have at least two alkylene groups and at least one thioether group, preferably at least two thioether groups, and at least one, preferably one thiol or thiolate group, which is usually a terminating thiol or thiolate group.
- the alkylene groups of the polyalkylenesulfides are preferably ethylene groups substituted by R 1 to R 4 .
- the thiocarbonate may comprise, for example, up to 1000, in particular up to 500, preferably up to 100 five-membered cyclic monothiocarbonate groups.
- Suitable thiocarbonates with one or more thiocarbonate groups and the synthesis thereof are described in WO 2019/034470 A1 and WO 2019/034473 A1.
- the thiocarbonate comprises 1 to 10, notably 1 to 5 five-membered cyclic monothiocarbonate groups. In a particularly preferred embodiment, the thiocarbonate comprises 1 or 2 five-membered cyclic monothiocarbonate groups. In a most preferred embodiment, the thiocarbonate comprises 1 five-membered cyclic monothiocarbonate group.
- the thiocarbonate may be a polymeric compound with high molecular weight.
- Preferred thiocarbonates have a molecular weight of up to 10000 g/mol, notably up to 5000 g/mol and particularly up to 1000 g/mol. Most preferred are thiocarbonates having a molecular weight of up to 500 g/mol.
- molecular weight means the number average molecular weight Mn, as determined by GPC against polystyrene as standard.
- a preferred thiocarbonate is a compound of formula (I)
- R 1 to R 4 independently from each other representing hydrogen or an organic group with up to 50 carbon atoms, whereby, alternatively, R 2 , R 4 and the two carbon atoms of the
- thiocarbonate ring may also together form a five to ten membered carbon ring.
- any of R 1 to R 4 represent an organic group
- such organic group is preferably an organic group with up to 30, more preferably up to 20 carbon atoms.
- R 2 and R 4 do not form a five to ten membered carbon ring together with the two carbon atoms of the thiocarbonate group.
- any of R 1 to R 4 represent an organic group
- such organic group may comprise heteroatoms and functional groups.
- it may comprise oxygen, sulfur, silicon and chloride.
- the organic group may comprise oxygen or chloride.
- chloride as used herein, is the trivial name of a covalently bound Cl atom.
- R 1 to R 4 may comprise oxygen, for example, in form of ether, hydroxy, aldehyde, keto or carboxy groups.
- the organic group is an aliphatic organic group with up to 30 carbon atoms which may comprise oxygen, nitrogen or chloride, in particular oxygen.
- R 5 to R 8 represent an aliphatic or aromatic group, which may comprise oxygen, for example, in form of ether groups.
- R 5 to R 8 represent an aliphatic hydrocarbon group, such as an alkyl group with 1 to 10 carbon atoms, an alkoxy group or a poly-alkoxy group.
- R 5 to R 8 represent an aliphatic hydrocarbon group, in particular an alkyl group with 1 to 10 carbon atoms.
- the organic group is a group -CH2-O-R 5 or a group
- two to four groups of R 1 to R 4 in formula (I) represent hydrogen, and the remaining groups R 1 to R 4 represent an organic group.
- R 1 to R 4 in formula (I) represent hydrogen
- the remaining group of R 1 to R 4 represents hydrogen or an organic group, preferably an organic group with up to 20 carbon atoms.
- R 1 or R 2 is the remaining group representing hydrogen or an organic group.
- R 1 is the remaining group representing hydrogen or an organic group.
- a most preferred thiocarbonate is a compound of formula (I), wherein at least three of the groups R 1 to R 4 are hydrogen, and the remaining group is hydrogen or a CrC4-alkyl group which is notably a methyl group.
- the thiocarbonate is a compound of formula (I), wherein R 1 is hydrogen or an alkyl group, notably a methyl group, and R 2 to R 4 are hydrogen.
- thiocarbonate shall include also mixtures of different thiocarbonates.
- the starters are selected from compounds with at least one thiol group, from compounds with at least one hydroxy group or from basic inorganic compounds.
- the starters do not comprise five- membered cyclic monothiocarbonate groups and do not correspond to the compound obtained by ring-opening of five-membered cyclic monothiocarbonate groups under decarboxylation.
- the starter does not comprise amino groups, preferably primary, secondary or tertiary amino groups, more preferably primary or secondary amino groups.
- the thiol group and the hydroxy group are, herein for short, commonly referred to as“reactive group”.
- the compounds with at least one thiol or hydroxy group are commonly shortly also referred to as“reactive compounds”.
- the reactive compound may comprise, for example, up to 1000, particularly up to 500 and preferably up to 100 reactive groups.
- the reactive compound comprises 1 to 10, notably 1 to 5 reactive groups selected from thiol groups, hydroxy groups or any combination thereof. In a particularly preferred embodiment, the reactive compound comprises 1 or 3 reactive groups selected from thiol groups, hydroxy groups or any combination thereof.
- the reactive compound comprises at least two reactive groups, notably with 2 to 5, more preferably with 2 to 3 reactive groups; the at least two reactive groups may be thiol groups, hydroxy groups or any combination thereof. In a most preferred embodiment, at least one of the at least two reactive groups is a thiol group.
- the reactive compound may be a polymeric compound with high molecular weight.
- Preferred reactive compounds have a molecular weight of up to 10000 g/mol, notably up to 5000 g/mol and particularly up to 1000 g/mol. Most preferred are reactive compounds having a molecular weight of up to 500 g/mol.
- the reactive group may also be obtained in situ, for example, in case of compounds with masked reactive groups or compounds comprising a precursor of the reactive group.
- the masked reactive group or precursor may be transformed into the reactive group in situ during the reaction.
- Reactive compounds with thiol groups are, for example,
- butanedithiol (ethyleneglycol-dimercaptopropylate); benzenedimethanethiol (isomers); 1 ,8- dimercapto-3,6-dioxaoctane; 2,3-dimercaptopropanol; 2,3-dimercapto-1-propanesulfonic acid (sodium salt); dimercaptosuccinic acid (salt); 2,2 ' -thiodiethanethiol; [1 ,T-biphenyl]-4,4 - dimethanethiol; dimercaptopropyl laurate; 2,2'-dimercaptoethyl-ether; 3,3'-dimercaptopropyl ether; dimercaptobenzene (isomers); biphenyl-dithiol; terphenyldithiol, or bi-thiophenyl sulfide (4,4-thiobisbenzenethiol);
- tri/tetra/oligo-thiols such as tri/tetra/oligo-thiols, for example, 1 ,2,3- trimercaptopropane; 2,3-bis[(2-mercaptoethyl)thio]-1-propanethiol; trimethylolpropane-tris-3- mercaptopropionate; pentaerythritol-tetrakis(3-mercaptopropionate); trimercaptotriazine; or capcure ® -type mercaptanes;
- mercaptoalcohols for example, mercaptoethanol, mercaptoglycerol, or mercaptophenol
- a compound with at least one thiol group, used as a starter is selected from the group consisting of methylmercaptan, ethylmercaptan; ethanedithiol; butanedithiol;
- dimercaptosuccinic acid salt
- dimercaptopropyl laurate 2,2'-dimercaptoethyl-ether; 3,3'-dimercaptopropyl ether;
- dimercaptobenzene derivatives
- biphenyl-dithiol terphenyldithiol, or bi-thiophenyl sulfide
- Preferred compounds are compounds of formulae
- Reactive compounds with hydroxy groups are, for example,
- - compounds with one or two hydroxy groups for example, CrC2o-alkanols, alkanediols such as ethylene glycol, propane-1 , 2-diol, propane-1 , 3-diol, butane-1 , 3-diol, butane-1 , 4-diol, pentane- 1 , 5-diol, neopentyl glycol, bis(hydroxymethyl)cyclohexanes such as 1 ,4-bis(hydroxymethyl)- cyclohexane, 2-methylpropane-1 , 3-diol, methylpentanediols, phenol, thiodiglycol, bisphenol A;
- alkanediols such as ethylene glycol, propane-1 , 2-diol, propane-1 , 3-diol, butane-1 , 3-diol, butane-1 , 4-diol, pentane- 1 , 5-diol,
- mercaptoalcohols for example, mercaptoethanol, mercaptoglycerol, or mercaptophenol
- - compounds with higher molecular weight such as, for example, di- or polyetherpolyols, di- or polyesterpolyols or polymers obtained by (co)polymerization of ethylenically unsaturated compounds with hydroxy groups or polyphenols;
- Preferred di- or polyesterpolyols have two to eight, preferably two to five hydroxy groups, more preferably two or three, in particular two hydroxy groups and are obtainable by reacting polyols, notably diols, with polycarboxyl ic acids, notably dicarboxylic acids.
- Preferred di- or polyetherpolyols have two to eight hydroxy groups, preferably two to five hydroxy groups, most preferably two hydroxy groups and are obtainable in particular by polymerizing ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, in the presence of a catalyst.
- Particularly preferred di- or polyetherpolyols have two to eight hydroxy groups, preferably two to five hydroxy groups, most preferably two hydroxy groups and are obtainable in particular by polymerizing ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, in the presence of a catalyst.
- polyetherpolyols are diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, and dibutylene glycol and polybutylene glycols.
- the starter may also be a basic inorganic compound, preferably a basic inorganic salt.
- Examples for such compounds are basic zeolites, metal oxides, metal hydroxides and metal sulfides, hydrotalcite, basic clays, and alkaline salts, including alkaline salts supported on oxides or resins.
- the basic inorganic compound is selected from inorganic salts such as metal hydroxides, metal sulfides, metal hydrogen sulfides, metal oxides, metal phosphates and metal silicates.
- inorganic salts such as metal hydroxides, metal sulfides, metal hydrogen sulfides, metal oxides, metal phosphates and metal silicates.
- the term“sulfide” includes mono-, oligo- and polysulfides of formula (S x ) 2 with x being an integral number of at least 1.
- the term“hydrogensulfides” includes mono-, oligo- and polyhydrogensulfides of formula (HS X ) 1 with x being an integral number of at least 1.
- metal hydroxides particularly preferred are metal hydroxides, metal sulfides and metal hydrogensulfides.
- the cation of the inorganic salt is preferably a cation with one or two positive charges, as, for example, an alkali or earth alkali cation. Most preferred is an alkali cation such as sodium or potassium.
- Examples of preferred inorganic salts are NaOH, Na S, K S X with x being 1 to 10.
- Preferred starters are inorganic basic compounds and reactive compounds with at least two reactive groups, notably with 2 to 5, more preferably with 2 to 3 reactive groups; the at least two reactive groups may be thiol groups, hydroxy groups or any combination thereof. In a more preferred embodiment, at least one of the at least two reactive groups is a thiol group.
- Most preferred starters are reactive compounds with at least two reactive groups, notably with 2 to 5, more preferably with 2 to 3 reactive groups; the at least two reactive groups may be thiol groups, hydroxy groups or any combination thereof. In a particularly preferred embodiment, at least one of the at least two reactive groups of the reactive compound is a thiol group.
- reaction schemes exemplarily show the reaction for specific starters and the thiocarbonate of formula (I) with Z being an alkyl group and X being the residual chemical group of the starter.
- a starter with a thiol group reacts with the thiocarbonate under decarboxylation as follows:
- the obtained compound may react with an integral number n of further thiocarbonate under decarboxylation to form a polyalkylenesulfide:
- the obtained compound may react with an integral number n of further thiocarbonate under decarboxylation to form a polyalkylenesulfide:
- Structural isomers which are usually less obtained are, for example, of formula Inorganic salts as starters also cause ring opening and decarboxylation of the thiocarbonate and give compounds with at least one alkylene group and at least one thiol or thiolate group.
- the hydroxy or thiol groups of the starter are transferred into the respective alkoxylate or thiolate groups before the reaction or by a catalyst used in the reaction.
- the reaction of starters with reactive groups (reactive compounds) and thiocarbonates is performed in the presence of a basic catalyst which forms a salt comprising the alcoholate anion or the thiolate anion derived from the starter.
- Suitable catalysts are notably basic catalysts, such as compounds with a tertiary amino group, a guanidino group, an amidine group or a phosphine group, or basic metals salts such as, for example, metal hydroxides and metal sulfides.
- the catalyst may be added before or during the reaction.
- the molar ratio of the reactive groups or of the inorganic salt to the thiocarbonate determines the molecular weight of the obtained product, as is obvious from the above reaction schemes.
- the obtained product is a mixture of compounds with different chain length and thus different molecular weight.
- the thiol groups tend to react first. Any selectivity regarding the thiol group can be augmented or damped by selecting suitable conditions and/or starting materials. A hydroxy group of low reactivity will usually promote the selectivity with respect to the thiol group while a less reactive (hindered) thiol group will favor a hydroxy group. Selecting a highly reactive thiocarbonate will usually suppress, preferably might suppress, any selectivity with respect to the thiol group.
- hydroxy group with low reactivity means a hydroxy group which reactivity is lower than a corresponding thiol group.
- the reaction may, for example, be performed at temperatures of from -20 to 250°C, preferably between 20 and 100°C.
- any activation energy for the reactions may be provided by high-energy radiation such as visible or UV light.
- the reaction occurs at 20 to 100°C without any further activation.
- a solvent may be used in the reaction.
- the use of a solvent may be helpful, in case that at least one of the compounds used is solid at room temperature (about 20-25°) and the other starting materials do act already as solvent for the solid compound.
- Suitable solvents are, for example, toluene, tetrahydrofuran and dimethylformamide. It is an advantage of the process that usually no additional solvent, preferably organic solvent, is required as the starting materials are usually liquid or at least one of the starting materials serves as solvent for any solid starting materials. If the starting materials are solid at room temperature, the reaction may be performed at temperatures above the melting point of any solid starting materials.
- a compound with at least one five-membered cyclic monothiocarbonate group is reacted with a starter selected from a compound with at least one thiol group, from a compound with at least one hydroxy group or from a basic inorganic compound,
- the whole amount of thiocarbonate used may be added to the reaction mixture in advance. If mixtures of different thiocarbonates are added, copolymers will be obtained.
- the thiocarbonate may also be added continuously or in certain increments during the reaction. As the
- the catalyst may be removed by suitable means, such as washing with water or an aqueous solution of acids such as hydrogen chloride.
- the compound obtained by the process is a compound with at least one alkylene group and at least one thiol or thiolate group.
- the thiol or thiolate group is the terminating group of the respective chain, see reaction schemes above.
- the possibility to have a terminating thiolate group is due to the preferred presence of the catalyst.
- several terminating thiol groups, respectively thiolate groups are formed accordingly.
- the at least two functional groups may be at least two thiol groups, respectively two thiolate groups if a starter with at least two reactive groups is used.
- the at least two functional groups may be at least one thiol, respectively one thiolate group and a further functional group that was part of the starter but was not affected by the reaction.
- Such functional group could be a hydroxy group of the starter with low reactivity or any other functional group such as alkoxy groups, amino groups or unsaturated groups, for example, vinyl groups, allyl groups, notably vinylether groups.
- the product of the reaction may be further reacted with a compound with at least one group that reacts with a thiol group -SH, shortly referred to as SH-reactive compound.
- SH- reactive compounds are, for example, mentioned in the non-published patent application PCT/EP2020/053083.
- the product of the reaction may be further reacted with a compound comprising at least one group that reacts with a further functional group of the starter.
- the process of the invention is an easy and economic process, performed in one highly selective reaction step.
- the process does not involve the handling of hazardous compounds such as COS.
- the process provides an easy access to variety of polyalkylenesulfides and allows the synthesis of copolymers, including block-copolymers, of a desired, predetermined structure and allows control over end group functionality.
- the process of this invention offers broad possibilities in synthesis as the direct products of the process may be easily further modified.
- M-CTC Compound of formula (I) wherein R 2 to R 4 are hydrogen and R 1 is methyl
- a figure shows the starting materials and the product. It is understood that the product is a mixture of structural isomers and polysulfides of different chain length. The figures show the main compound of the mixture of polysulfides obtained, only. In all examples, the conversion to polysulfides was complete, the starter and the thiocarbonate were fully consumed and reacted to polysulfides without any significant formation of by products.
- Benzene dithiol 500 mg, 3.52 mmol
- CTC 1456 mg, 14 mmol, 4 eq.
- DBU was then added (50 mg, 0.32 mmol), and the reaction was stirred at 60°C overnight.
- Benzene dithiol 500 mg, 3.52 mmol
- CTC 1456 mg, 14 mmol, 4 eq.
- NaOH was then added (10 mg, 0.25 mmol), and the reaction was stirred at 60°C overnight.
- Benzene dithiol 500 mg, 3.52 mmol
- CTC 1456 mg, 14 mmol, 4 eq.
- K2S X was then added (20 mg, 0.18 mmol), and the reaction was stirred at 60°C overnight.
- Benzene dithiol 500 g, 3.52 mmol
- CTC 1456 mg, 14 mmol, 4 eq.
- DMP 30 was then added (20 mg, 0,08 mmol), and the reaction was stirred at 60°C overnight.
- Benzene dithiol 500 mg, 3.52 mmol
- M-CTC 1650 mg, 14 mmol, 4 eq.
- DBU was then added (50 mg, 0.32 mmol), and the reaction was stirred at 60°C overnight.
- Example 6 Benzene dithiol (500 mg, 3.52 mmol) and CTC (1456 mg, 14 mmol, 4 eq.) were stirred together at room temperature without any solvents to obtain a homogenous solution. DBU was then added (50 mg, 0.32 mmol), and the reaction was stirred at 60°C. After one night it resulted from GC-MS that all the CTC was consumed, and then M-CTC (825 mg, 7 mmol, 2 eq.) was added to the solution. After another night at 60 °C all of the M-CTC was also consumed, and further CTC (1456 mg, 14 mmol, 4 eq.) was added again. A white polymer was obtained after nearly an hour.
- Benzene dithiol 500 mg, 3.52 mmol
- M-CTC 825 mg, 7 mmol, 2 eq.
- DBU was then added (50 mg, 0.32 mmol), and the reaction was stirred at 60°C overnight. After one night it resulted from GC-MS that all the M-CTC was consumed, and then CTC (1456 mg, 14 mmol, 4 eq.) was added to the solution. After a few hours a suspension of a white polymer was obtained.
- a liquid polymer has been obtained.
- trimercaptan 500 mg, 1.92 mmol
- CTC 1200 mg, 11.54 mmol, 6 eq.
- DBU was then added (25 mg, 0.16 mmol), and the reaction was stirred at 60°C overnight.
- the GC-MS showed that all the CTC was consumed.
- Ethane dithiol (330 mg, 3.51 mmol) and M-CTC (1700 mg, 14.40 mmol, 4 eq.) were stirred together at room temperature without any solvents to obtain a homogenous solution.
- DBU was then added (25 mg, 0.16 mmol), and the reaction was stirred at 60°C overnight.
- Example 11 M-CTC (1650 mg, 14 mmol, 4 eq.) and Na2S (15 mg, 0.20 mmol) were stirred at room temperature without any solvent for 1 hour, and then the reaction mixture was heated at 60°C overnight.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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EP19171361.9A EP3730478A1 (de) | 2019-04-26 | 2019-04-26 | Verfahren zur herstellung von verbindungen mit mindestens einer alkylengruppe und mindestens einer thiol- oder thiolatgruppe |
PCT/EP2020/061400 WO2020216873A1 (en) | 2019-04-26 | 2020-04-23 | Process for the preparation of compounds with at least one alkylene group and at least one thiol or thiolate group |
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EP20720449.6A Pending EP3959194A1 (de) | 2019-04-26 | 2020-04-23 | Verfahren zur herstellung von verbindungen mit mindestens einer alkylengruppe und mindestens einer thiol- oder thiolatgruppe |
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US3232936A (en) * | 1961-04-26 | 1966-02-01 | Eastman Kodak Co | Mercaptoethylation of amines with carbamates |
US3624052A (en) | 1962-01-08 | 1971-11-30 | Thiokol Chemical Corp | High molecular weight poly(propylene sulfide) |
BE626970A (de) * | 1962-01-12 | |||
FR1431717A (fr) * | 1964-12-23 | 1966-03-18 | Aquitaine Petrole | Procédé de préparation des alpha-dithiols |
US6525168B2 (en) | 2000-03-09 | 2003-02-25 | Pbt Brands, Inc. | Chemically resistant polythiothers and formation thereof |
WO2014031181A1 (en) * | 2012-04-25 | 2014-02-27 | Dow Global Technologies Llc | Polyurethanes made using bismuth thiocarbamate or thiocarbonate salts as catalysts |
CN102746476B (zh) * | 2012-06-18 | 2014-04-23 | 浙江理工大学 | 含环氧基团的三硫代碳酸酯化合物及其制备方法和应用 |
CN111032736A (zh) | 2017-08-17 | 2020-04-17 | 巴斯夫欧洲公司 | 制备具有氨基甲酸酯基团的聚合物的方法 |
WO2019034473A1 (en) | 2017-08-17 | 2019-02-21 | Basf Se | PROCESS FOR PRODUCING A POLYMER HAVING URETHAN GROUPS |
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2019
- 2019-04-26 EP EP19171361.9A patent/EP3730478A1/de not_active Withdrawn
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2020
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- 2020-04-23 EP EP20720449.6A patent/EP3959194A1/de active Pending
- 2020-04-23 KR KR1020217034082A patent/KR20220004032A/ko unknown
- 2020-04-23 WO PCT/EP2020/061400 patent/WO2020216873A1/en unknown
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CN113727965A (zh) | 2021-11-30 |
KR20220004032A (ko) | 2022-01-11 |
JP2022531565A (ja) | 2022-07-07 |
US11814344B2 (en) | 2023-11-14 |
US20220185773A1 (en) | 2022-06-16 |
WO2020216873A1 (en) | 2020-10-29 |
EP3730478A1 (de) | 2020-10-28 |
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